Compositions of matter comprising acetone-formaldehyde reaction products and liquid polysulphide polymers



Mortimer T. Harvey, South Orange, and Peter L. Rosamilia, Newark, N. J.,assiguors to Harvel Research Corporation, a corporation of New Jersey NDrawing. Application June 30, 1953 Serial No. 365,251

5 Claims. (Cl. 260-42) This invention relates to novel compositions ofmatter and to methods for preparing them as well as to articles nitedStates Patent about 210 F. When the temperature of the reacting ofmanufacture in which one or a combination of two or more of them may beemployed as components. In one of its more specific aspects, theinvention is directed to improving certain properties of variousThiokols.

In the course of our experimentations with normally liquid polymers ofThiokol having an average molecular weight between about 300 and 4,000and available on the market as Thiokol liquid polymer ZL-l00, LP-3, andLP-2, we have discovered that by combining therewithacetone-formaldehyde resinous reaction products and such combinationsare converted to the substantially solid state, there may be producedsubstantially solid or rubbery products which have high heat resistancecharacteristics. We have discovered that the use of suchacetoneformaldehyde resinous reaction products combined with saidpolymers and converted to the substantially solid or rubbery statesurprisingly imparts to the mass exceptional resistance to fusion atrelatively high temperature when compared with the temperature of fusionof said polymers converted to the substantially solid or rubbery statebut in the absence of said acetone-formaldehyde resinous reactionproducts.

The Thiokol liquid polymers employed herein in the practice 'of thisinvention are those of such chemical structure that the repeating unitin the polymer chain is -SSCH CH OCH OCH CH and the terminals being thereactive SH groups. These liquid polymers can be classified as polymericdimercaptans. The acetone-formaldehyde resinous organic reactionproducts may be produced by reacting acetone and formaldehyde to whichhas been added a quantity of an alkaline catalyst, for example sodiumhydroxide, potassium hydroxide and the like. The ratio of acetone toformaldehyde employed in the reaction is in the proportion of 1 mole ofacetone to 26 moles of formaldehyde.

The general procedure which is employed in the production of theacetone-formaldehydereactionproducts is as follows:

Example 1 (1 mole acetone to 2-6 moles formaldehyde) Employing a closedsteel kettle with a scraper agitator anda reflux condenser, there isheated while the scraping stirrer is in motion all of the acetone andformaldehyde which is in aqueous solution. In a separate container thereis prepared an aqueous solution of the reguired amount of alkalinecatalyst to be employed. One quarter of the alkaline solution is addedto the agitated acetone and formaldehyde mixture. Then steam is appliedto the jacket of the reaction vessel for a short period of timewhereupon an exothermic reaction between the acetone and formaldehyde isinitiated. The steam is cut off when the temperature of the mass reachesapproximately 120- 135" F. and the cold water is passed through thejacket to maintain the temperature of the reacting mass, which isproceeding exothermically, at a value no greater than mass falls toabout 140 F. due to the continued cold water flow through the jacket,the second one-quarter of the aqueous solution of alkali is added andthe reaction again proceeds violently exothermically and the temperaturerises and then drops. When it again reaches a value of approximately 140F., the same procedure is followed in adding the last two one-quartersof the aqueous alkaline solution. After the last one-quarter of aqueousalkaline solution has been added and the subsequent exothermic reactionhas taken place, the mass is no longer alkaline and its temperature hasdropped to about 140 F. Then the mass is dehydrated under reducedpressure conditions. This may be accomplished by heating the mass up toa temperature of approximately 160-175 F. while under a vacuum ofapproximately 29" of mercury, when the resultant mass will be found toto a substantially anhydrous, resinous acetone-formaldehyde reactionproduct. Such organic reaction mass is characterized as being afree-flowing liquid resinous mass which when mixed with 20 parts byweight of a l-l aqueous dispersion of lime per 100 parts by weightthereof will be converted at room temperature when allowed to standovernight to the solid, substantially infusible state.

Example 2 (1 mole acetone to 3 moles formaldehyde) Following the sameprocedure as that set forth in EX- ample 1 and employing 30 parts byweight of acetone and 126 parts by weight of an aqueous solution offormaldehyde (37% concentration) and approximately 2 parts of sodiumhydroxide in 4 parts of water, there is produced a substantiallyanhydrous acetone-formaldehyde organic reaction mass hereinafter knownas Product AF-l.

Example 3 (1 mole acetone to 4 moles of formaldehyde) Example 4 (1 moleof acetone to 5 moles of formaldehyde) Employing the same procedure asthat set forth in Example 1 and'using 30 parts by weight of acetone and212 parts by weight of an aqueous solution of formaldehyde (37%concentration) and approximately 4 parts of sodium hydroxide in 8 partsof water, there is produced an acetone-formaldehyde organic reactionmass hereinafter'known as Product AF-3.

. According to this invention, one or a combination of condensing agent,the ratio of acetone to formaldehyde being within the limits heretoforeset forth and examples of which are Products AF-l, AF-2, and AF-3, maybe combined with said Thick-o1 liquid polymers. Such combinations whichare normally liquid may be converted to the substantially solid state byadding thereto a curing agent, examples of which are the metallic oxidesin the presence of hexamethylene tetramine as well as the organicperoxides, examples of which are zinc oxide and hexamethylene tetramine,lead peroxide alone, benzoyl peroxide, tertiary butyl hydroperoxide,tertiary butyl perbenzoate and cumene hydroperoxide. In general, theratio by weight of the Thiokol liquid polymers to the Patented Jan. 7,1958 acetone-formaldehyde reaction mass is in the range of 100 parts ofthe formerto -100 parts of the latter; In producing these normally solidcompositions of this invention, weprefer to employ lead peroxide as thecuring agent and for purposes we employ approximately 7.5-15' partsthereof for each 100parts of thecombined weights of the Thiokol liquidpolymer. and the acetone-formaldehyde reaction masses used. Suchtri-component mixtures may be allowed mately 72 hours and at the end ofthat period theoriginally liquid mass will be found to have to thesubstantially solid state whose rubbery nature may vary depending uponthe proportion of acetone-formaldehyde organic reaction massemployed.

Example 5 80 parts of Thiokol liquid polymer LP-Z (average molecularweight approximately 4000) and 20-parts of Product AF-2 and 7.5 parts oflead'peroxidewere mixed togethertouniformityandallowed to stand at roomtemperature for 72 hours.

mass was found to have been converted to the substantially solidandrubbery state andhereinafter isknown as TAF1. Simultaneously 100partsof Thiokol'liquid polymer LP-2 and 7.5 parts of lead peroxide weremixed together and allowed to stand at room temperature for 72'hours. Atthe end of thatperiod, this product was found tobe a substantially solidrubbery mass and was used as a control for comparison and is hereinafterknown as Product CT. A sample of Product CT and a like size sample ofTAF-l wereplaced in an oven maintained at a temperature of;500 F.v Theywerezallowed to remain there for a period of 5-15 .minutes .after whichthey were examined. Examination. revealed: that thev sample; of CT had,fused and flowed whereas Sample TAF-1Jmaintained .itsoriginal. form, hadnotfused and was ,still in the substantially solidi rubbery mass.

Example 6 Following the same procedureas before and using 70 parts ofThiokol liquid polymer ZL100 (average molecularweight about'300); 30parts of Product AF-3 and. parts ofleadrperoxide, there. wasproducedajsubstantially solid rubbery mass hereinafterrknown as TAR-2having high heatresistance characteristics.

Example 7 examples'havexbeenw given merely by way 'of,illustration;and;are in no WayJ be-taken by way of limitation; The proportions ofthe. Thiokol liquid polymer to acetone-formaldehyde reaction mass maybewaried within-' the: limits, hereinbefore setforth to. obtain novel:and.

highly useful products, and the'particularcacetoneeformale dehydereaction masses may- 31501b6-1V3Il6d With 11131118 ranges of thoseheretofore set forth as rmay be .theiparticm lar curing agent andquantities thereof.

to stand for a period of approxi been converted" At the end of thatperiod, the- The novel combinations of the Thiokol liquidpolymerstogetherwith the acetone-formaldehyde reaction masses and curingagent therein may be used as casting media, coating media or applied inany other manner and thereafter set at room temperature to provide awide variety of highly useful articles of manufacture such as hose,.belts; resinous-coverings and coatings where chemicalandrheat resistance.are required;

SuchLcombination may be spread as a thin layer onto a subdecking or.flooring and allowed toset to provide chemical? and" heatresistant'floor covering. They may also beused'as laminating-materials and'forvarious other purposes for which such liquid polymers have heretoforebeen employed.

It is to be understood that' the following claims are intended to coverall the generic and specific features of the invention herein describedand all statements of the scope of the invention which as a matter oflanguage mightbe' said to' fall therelietween; and that they areintended'ro'be inclusive in s'cope'and not exclusive, in

that, if desired, othermaterials may bea'ddedto my novel composition ofmatter herein claimed without' departing Particularly it is to from the"spirit" of 'the invention. be understood that iii-said claims,ingredients or componentsrecited in the siirgular are intended toinclude compatiblmmixtures of"said ingredients wherever the sensepermits:

1. A novel eornposititm ofmatter'comprisingthe combination of- (*I*) a"normally liquidpolymer which in chemical structure has therepeatingunitof andtheterminals being thesH groups, and (II) acetone formaldehyde"resinous 1 organic reaction mass 1 produced 1 byreacting acetone and 1formaldehyde in the mole'ratio of 1 of th'e former to 2-"6 of*the latterin the presence of an alkalineagent;jthewratio by weight of (-I) to-(II)being partsnof ()[to 5'-l00 parts of (II);

2. A novel composition of'mattercomprisinga combination definedin elaim1; said combination-convertedwith the mole ratio -of acetoneto'formaldehyde being 1 of the. formerto approximately 4=ofthe latter.

5. A novel'composition of matter defined in-claim l with saidv normallyliquid polymer having an average molecular weight :of1approximately4000.

References Cited-in the -fileof'this patent UNITED STATES PATENTS2,410,623? Ballardet alt- Nov. 5; 1946 2,466,963 Patrick et al Apr; 12,1949 OTHER REFERENCES Fisher: Ind. Eng. Chem., 31, 941-945 (1939).Thiok'ol LiqUid POIym'er LP-Q (1948), publication of the ThiOkQlCor-poration',Trenton; NewJersey, 18 pages.

1. A NOVEL COMPOSITION OF MATTER COMPRISING THE COMBINATION OF (I) ANORMALLY LIQUID POLYMER WHICH IN CHEMICAL STRUCTURE HAS THE REPEATINGUNIT OF